N-substituted fatty acid amide lubricants

ABSTRACT

1. THE COMPOUND N,N-DIBUTYL-(9(10)HYDROXY-(9) 10DIBUTYLPHOSPHATO)STEARAMIDE.

United States Patent Oifice 3,849,454 Patented Nov. 19, 1974 U.S. Cl. 260-403 1 Claim ABSTRACT OF THE DISCLOSURE This invention relates to N-acylmorpholines and N- mono and N,N-disubstituted fatty acid amides and to similar derivatives of epithioamides which are useful as base and extreme pressure lubricants and additives.

This is a division of application Ser. No. 176,734, filed Aug. 31, 1971.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to certain compounds which are N-fatty acyl derivatives of primary and secondary amine and N-substituted acyl derivatives of primary and secondary amines which have exhibited utility as base lubricants, extreme pressure lubricants or lube additives. More particularly, this invention relates to N- and NN- disubstituted long chain aliphatic amides the acyl corm ponent of which is a normal, branched, or substituted alkenoic ar alkanoic acyl group containing from 16 to 22 carbon atoms the amide nitrogen of which may be derived from an alkyl amine, dialkyl amine, alkylalkoxyalkylamine, dialkaoxyalkylamine or nitrogen heteroalicyclic. Typical amines are butylamines, dibutylamines, N- methyl-alkoxyethyl amine, di-ethoxyethyl amine, and morpholine. The acyl substituent referred to may be divalent sulfur or pentavalent phosphorous.

We have discovered that many of the simple N-alkyl and N,N-dialkyl or N-alkyl-N-alkoxyalkyl amides of the C to C alkeneoic or alkanoic fatty acids are good base lubricants. We have further discovered that the introduction of divalent sulfur into the fatty acid moiety imparts excellent extreme pressure lubricant characteristics to such compounds. In particular we have found the epithio group to be most effective. We have also observed that the introduction of both hydroxy and alkyl phosphato groupings alpha to each other also imparts extreme pressure lubricant characteristics to the compound.

In addition it was noted that the above hydroxy-phosphato compound and its mercapto analog N-[9(10-mercapto- (9) 10-dibutylphosphato] stearamide were effective antiwear compounds and additives.

Included among the specific compounds operable as base lubricants are N-methyl-N-butyloleamide, N-ethoxyethoxyethoxy propyloleamide, N-ethoxyethoxy propyloleamide, N-methoxyisopropyloleamide, N-methoxyethyloleamide. Compounds showing particular promise as extreme pressure lubricants or additives are N,N-dibu'tyl-9, l0-epithio stearamide,

N,N-dibutyl-9, 1 0-12, 1 3-diepithiostearmide,

9, l O-epithioste aroyl morpholine, N-ethoxyethoxyethoxypropyl-9, 10- epithio stearamide, N-9, 10-12, 1 3-diepithio stearoylmorpholine, and

N- [9 10) -hydroxy-9 10)-dibutylphosphato] stearamide.

I Compounds showing particular promise a antiwear additives are N,N-dibutyl-[9(l0)-hydroxy-(9) IO-dibutylphosphato]stearamide and N,N-[9(l0)-mercapto-(9)l0- dibutylphosphatostearoyl] morpholine.

EXAMPLE 1 N-methyl-N-butyloleamide grams (0.33 mole) of oleoyl chloride was added dropwise and with stirring to a mixture of 29 grams (0.33 mole) of N-methyl-N-butylamine and 27 grams (0.33 mole) of pyridine. Stirring was continued until the heat of reaction subsided. The solid pyridine hydrochloride was filtered oif and the filtrate was washed successively with aqueous HCl until acid free. It was dried stripped, percolated through an activated alumina column, and the product removed from the percolate by stripping off the solvent. Analysis of the product: Percent C, 78.87 (theory 78.63); percent H, 13.02 (theory 12.82); percent, N, 3.96 (theory 3.99).

EXAMPLE 2 N,N-dibutyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride 42.5 grams (0.33 mole) of di-n-butylamine and 27 grams (0.33 mole) pyridine. Analysis of the product: Percent C, 78.94 (theory 79.25); percent H, 13.16 (theory 13.06); percent N, 3.44 (theory 3.56) confirm the preparation.

EXAMPLE 3 Ethoxyethoxyethoxy propyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 73.0 grams (0.33 mole) ethoxyethoxyethoxypropylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 71.85 (theory 72.04); H, 11.80 (theory 11.80), and N, 2.96 (theory 2.90) confirm the preparation.

EXAMPLE 4 Ethoxyethoxypropyloleamide This material was prepared by the procedure of Example 1 from grams (0.33 mole) of oleoyl chloride, 58.3 grams (0.33 mole) ethoxyethoxypropylamine and 27.0 grams (0.33 mole) of pyridine. Analysis of percent C, 71.45 (theory 73.80); percent H, 11.87 (theory 12.07); and percent N, 2.92 (theory 3.18) confirm the preparation.

EXAMPLE 5 Methoxyisopropyloloeamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 29.3 grams (0.33 mole) methoxyisopropylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 73.15 (theory 74.99); percent H, 12.01 (theory 11.93); and percent N, 3.67 (theory 3.97) confirm the preparation.

3 EXAMPLE 6 Methoxyethyloleamide This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 24.4 grams (0.33 mole) of methoxyethylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 73.08 (theory 74.55); percent H, 11.98 (theory 11.83); and percent N, 3.31 (theory 4.14) confirm the preparation.

EXAMPLE 7 Oleoylmorpholine This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 28.7 grams (0.33 mole) of morpholine and 27.0 grams (0.33 mole) of pyridine.

EXAMPLE 8 N,N-dibutyloleamide This product was prepared following the exact procedure of Example 2 except for the substitution of oleoyl chloride by linoleoyl chloride.

EXAMPLE 9 N,N-dibutyl-9,10-epithiostearamide 120 grams (0.30 mole) of N,N-dibutyloleamide was epoxidized by the addition with stirring of 62.0 grams (0.36 mole) of meta-chloroperbenzoic acid in 630 ml. of chloroform. Reaction was continued for 1 hour beyond final addition and the excess peracid destroyed by a small amount of a 10% solution of Na SO The meta-chlorobenzoic acid was removed by a NaHCO wash, followed 'by water washing. The CHCl solution was then dried with anhydrous Na SO and the CHCl stripped off to recover the product N,N-dibutyl 9,10 epoxystearamide, oxirane content 3.45% (theory 3.91%). 100 grams (0.24 mole) of this product was added to a well stirred slurry of 55.7 g. (0.75 mole) of thiourea and 89.5 g. (0.72 mole) of benzoic acid in acetone. Stirring was continued for 3 hours beyond the terminal addition whereupon the benzoic acid was washed out with 38.8 g. (0.36 mole) of Na CO and the organic product extracted with hexane. The organic phase extract was dried and stripped to recover the product N,N-dibutyl 9,10 epithiostearamide containing 6.41% sulfur (theory 6.67%).

EXAMPLE 10 N-(9,10-epithiostearoyl)morpholine EXAMPLE 11 N,N-dibutyl-9,10-12,13-diepithiostearamide This product was prepared following the procedure described in Example 9 except for the replacement of the N,N-dibutyloleamide of Example 9 by N,N-dibutyllinoleamide, and a doubling of the molar ratios of all reagents. The product analyzed as follows: percent C, 69.64 (theory 68.57); percent H, 10.93 (theory 10.76); percent N, 3.10 (theory 3.07); percent S, 11.7 (theory 14.06).

EXAMPLE 12 N-ethoxyethoxyethoxypropyl-9, 1 O-epithioste aramide To 166 g. of N ethoxyethoxyethoxypropyl oleamide,

Example 3, was added dropwise and with stirring 73.8 g.

of m-chloroperbenzoic acid in 800 ml. of CHCl The spent m-chloroperbenzoic acid was removed with 10% aqueous NaHCO and the epoxide recovered by drying and stripping 011 the CHCl 171 g. of this epoxide was added dropwise to a slurry of 56 g. thiourea in 1000 ml. of acetone and the concurrent addition of 43.4 g. of glacial acetic acid and the reaction mixture stirred for 3 hours. The glacial acetic acid was neutralized with Na CO and the episulfide, N-ethoxyethoxyethoxypropyl- 9,10-epithiostearamide, extracted with Skellysolve B and washed, dried, and stripped. Its elemental analysis was C=67.1 (66.52), H:11.42 (10.88), N=2.67 (2.87), 5:2.29 (6.57).

EXAMPLE 13 N-ethoxyethoxyethoxypropyl-9 10 -mercaptostearamide 173 g. of N ethoxyethoxyethoxypropyloleamide in CCl was treated in the cold with a CCl solution containing 60.9 g. of bromine. Any unreacted bromine was removed by a thiosulfate wash. 140 g. of the resulting dibromo compound was added dropwise to a well stirred solution of 72 g. of Na S-9H O in dimethylsulfoxide maintained at C. Stirring was continued at 80 C. for 3 hours. Water was added and the reaction product was extracted with hexane; washed, dried, and stripped. Elemental analysis of the product was C=66.3 (66.5); H=11.1 (10.9); N=2.7 (2.9); S=4.4 (6.8).

EXAMPLE 14 N,N-dibutyl-9 10) [dibutylphosphono stearamide g. of N,N-dibutyloleamide, Example 2, 148 g. of dibutyl phosphite, and 1.29 g. of benzoyl peroxide catalyst were heated at C. for 3 /2 hours. Additional units of 1.29 g. of benzoyl peroxide was added after the first and second hours of reaction time. The excess dibutyl phosphite was then removed by distillation at reduced pressure, 0.45 mm. Hg. The stillpot contents showed strong adsorption bonds at 8, 9.3, and 9.7 microns characteristics of the phosphonate group. The elemental analysis was C=obs. 71.46 (69.50); H=obs. 12.42 (11.92); N=obs. 2.20 (2.38); P=obs. 4.24 (5.28) percent respectively.

EXAMPLE 15 N-9,10-12,13-diepithiostearoylmorpholine This product was prepared by the same procedure described in Example 9 except for the substitution of linoleoyl morpholine for the N,N-dibutyloleamide of Example 8 and the doubling of molar proportions of the mchloroperbenzoic acid in the epoxidation step and the thiourea and benzoic acid in the epithioation step. The elemental analysis was C=obs. 68.89 (63.92); H:obs. 10.26 (9.44); N=obs. 3.29 (3.38); S=obs. 4.00 (15.49) percent respectively.

EXAMPLE 16 N,N-dibutyl- [9 10) -hydroxy- 9) 10-dibutylphosphato] stearamide EXAMPLE 17 N-[9(10)mercapto-(9) 10-dibutylphosphatostearoyl] morpholine 12 g. of dibutylhydrogen phosphate was added dropwise with stirring to 51.0 g. of (9,lO-epithiostearoyl)morpholine, the preparation of Example 10, at 8590 C. and the heating and stirring continued for 3 hours beyond the It can be seen from the data presented that the N- termmal addition. The reaction product was dissolved in alkoxyalkyl nd N,N-di(alkoxyalkyDoleamides, without commercial hexane and any excess or unreacted the assistance of additives, exhibited wear characteristics H 5 (i.e., low scar diameters) comparable to the commercial HO P (0O4H)@ controls Aeroshell and Gulfpride, which do contain addiwas neutrallzed and washed out with aqueous ti to improve performance 1 9 10 .h

NaHCO The hexane extract was washed several times with water dried and stripped. The elemental analysis of droxy-(9) l0-dibutylphosphato] stearamide and N- [9 10) the product was czorbsh 66.74 (6936); H=obs 1069 mercapto (9)10 dibutylphosphatostearoyl]morpholine (11.05); N=obs. 2.89 (3.32); S=obs. 3.27 (2.17); not only exhibit low wear characteristics in themselves but bS- 1.68 Percellt fespectivelyalso impart as additives such characteristics to paraifin oil EXAMPLE 18 and DOS base lubricants.

The compounds prepared in accordance to the pro- EXAMPLE 19 cedures given in Examples 1 through 7 were evaluated as base lubricants in the Shell Four-Ball Wear tests follow- The various amides were evaluated as extreme pressure mg a modified procedure of ASTM 13226647 The lubricants or additives in a Shell 4-ball extreme pressure sulting scar diameter on the balls after running at 600 tester a1 1440 P-P' following ASTM Procedure D2596 rpm. for 1 hour at 120 C. and 50 kg. load were com- 67T. Loads were increased in increments of kg. to weld pared with the scars obtained us1ng commercial lubricants point and the test ran for one minute or to weld Whichever such as Aeroshell M1l-L-708 (d1-2-ethylhexyl sebacate occurred first Commercial h oid fluid SAE was and additive), Gulfpride, single G, MS, multrvlscosity, yp and 100 ffi oiL The results f these tests are employed as the control E.P. lubricant. The performance reported 1n Table I. of the amides tested is given 1n Tables 11, III, and IV.

TABLE I Antiwear lubricant properties of fatty acid amides Average wear scar, mm.

Without With 5% Compound additive additive Additive 1 N,N-bis(lethoxyethyboleamide- 0.597 N,N-di-butyl9,10-epithiostearamide N,N-di-n-butyl-9,lo-epithiostearamide. 0. 842 None Oleoylmorpholine 0. 623 Do N,N-dimethylnleamide 0. 797 D0 N,N-din-propylo1eamide 0. 908 Do N,N-di-n-hexylo1eamide 0. 893 Do N,N-di-n-butylemcamide 0.758 Do 8 Ngiidi-mbaityl amide of sel. hydrogenated cottonseed 0.798 Do a 3; ac: s. 9 N,N-bis(2-methoxyethyl)oleamide. 0.626 Do 10- N,N-dibntyloleamide 0. 710 11 N-oleoylA-propylpiperidine. 0. 847 12 M01 pholide of sel hydrogena 0. 642 1 N-methyl-N-butyloleannde 0. 607 1 N-ethoxyethoxyethoxypropyole 0. 503 1 N-ethoxyethoxypropyloleamide- 0. 526 1 N-methoxyisopropyloleamide. 0. 705 1 N-methoxyethyloleamide 0. 420 18 102 see. paraifin 011. N -methoxyethyloleamide 19- D.O.S D0 20 N,N-dibutyl-9(10)carbobntoxyoctadeeanamide- 21 102 sec. paraffin oil- N,N-dibuty1-9 (10)-earbobutoxyoctadecanamide 22 D.O.S 5 Do 23 N-[9(10)mercapto-(9)10-dibutylphosphatostearoyl morpholine. 24 102 sec. parafi'in 011.. N-[9(10)mercapto-(9)10-dibutylphosphetostearoyl] morpholine 25 D.O.S Do 26 N,N-dibutyl-[9(10)-hydroxy-(9)IO-dibntylphosphatostearamide. 27 102 sec. parafliu 011-. N,N-dibutyl-[9 (10)-hydroxy-(9) IO-di-butylphosphato] stearamide.

28 D.O.S 29 N,N-dibutyl-9(l0)-[dibutylphosphono] stearamide.

31 N-ethoxyethoxyethoxypropyl9(10)mercapt0stea1amide 32 N-(Q,10-12,13-diepithiostearoyl)morpholine 33--. BiSQFethylheXyDSebacate 34 100 sec. paraffin oil 35.-. Aero Shell (Mil-7808) 36 Gulf Pride, single G, MS, multiviscosity 37 100 see. paraflln oil- N,N-dibutyl-9,10-12,13-diepithiostearamide. 38 Bis (2-ethylhexyl)sebacate 6 Do.

39... 100 sec. paraffin oil 0. 723 N-9,l0 epithiostearoyl morpholine. 40 Bis(Z-ethylhexyDsebacate 0. 915 D0.

41.-. sec. paraifin 011.. 0.917 N,Ndibutyl-9,10-dichlorostearamide. Q Bis(2-ethylhexy1) sebacate 0. 848 Do.

TABLE II Extreme pressure tests on N-(O,10-12,13-diepitliiostearoyl)morplio1ino (PC-O-No. 7684) Extreme pressure tests (ASTM D2596-67'I) Applied Average scar W e1d W Base 011 Additive load, kg. mn point P011111; 110 addi- \vitl 7684 None 200 2.21. Compound tive) None 260 2.38. None 340 2.43.

l N.N-bis(2-ethoxyetliyl) oleamide 120 170 None 400 175, N,N-di-n-butyl-9,IO-epithiostearamido. 300 None 4130 2.90, Oleoylmorpholine 120 150 None 500 2.03. N,Ndinietliyloleamide 120 140 N,N-di-n-propyloleamido 100 2.23. N,N-di -n-hexyloleaniide. 120 2.61. N,N-di-n-butylerueoniide 130 2.74. N,N-di-n-buty1 amide oi hydrogenated 140 Weld.

cottonseed fatty acids N,N-bis(2-metlioxyet1iyl)oleamide 120 2.54. N-nietliylN-butyloleamide 140 2.58. N,N-dibutyl-S),10-epitliiostearamide 7684 (5%) 150 Weld. N,N-dibutyl-S),10-12,13-diepitl1iostearamide N-nictlioxyetliylole 7684 (5%) 140 2.53. N-ethoxyethoxyethoxylpropyloleamide D 160 2.77. N-ethoxyetlioxypropyloleamide Do 7684 (5%) 170 Weld N -metl1oxyisopropy1oleamide N-metlioxyethyloleamide N-9,10-epithiostearoylmorpholiile Bis(2-etliy1hexyl)sebacate 100 see. paraffin oil SAE #90 commercial hypoidffiuid TABLE III Extreme pressure tests on N,N-dlbutyl9(10)-(dibutylph0spli0u0) Evaluation of N,N-dibutyl-9,1012, l3-di-epitliiostearamide as an steai'amide (P additive and as a base oil in extreme pressure tests. (ASTM D2596-G7T) I 2 i Applied Averagesear, Percent L d k W Base oil Additive load, kg. min. .mm. Base 011 additive 0a g ear-scar 7685 gone 120 3.05 5 140 1.90. One 140 4.50. 3 3521 $5 72; 200 2.35. None 150 Weld.

(5%) 220 2.75. (5%) 240 We1d,5sec. 3O

120 1.51. (5%) 180 1.59. (5%) u 100 2.47. (5%) 200 Weld,4sec. (0%) Extreme pressure tes s on NN-dibutyl-[9(10)-h (lror '-9(10)dibut l- (10 7) 260 3.55. x Y 5 (107:) 270 Weld 10 sea 3, phosplmtolstearamide (PC 0 No. 7686) A r N,N-dibutyl-QJO-12J3- None 120 1.33. Baseou Additive i g gf n diepithiostearamide. N 160 161 1 b one None 200 1.89. 3- 3 None 280 2.13. 340 None 320 2.47. 350 None 360 2.70. 360 W012i None 400 2.88. None 440 Weld, 46 sec. 120 2.28. 140 2.80. lneipient seizure. 150 3.01

. 1 Extreme pressure tests on N etlioxyetliosyethoxypropylD,10+pi- 160 eld.

tliiostearnmide (P C-O-No. 7682) 120 1 Applied Avei'agescer 140 2.85. Base 011 Additive load, kg. m None 1.05.

None 160 1.75. None 240 2.35. 50 None 300 2.19. None 340 2.55. None 360 2.62. None 380 Weld,

102 93mm on 7682 (5%) 120 Extreme pressure tests on N-[9(10)-meicapt0-Q( )-dib t h 1 t 7682 Weld 50 stearoyl.]moiplioline (0C 0 No. 7081) Applied Averagescar 7682 (57) 120 2.23. i 7682 5 140 2'44. Base oil Additive load,kg. mm. 7682 (5%) 150 None 120 0.608.

gone 1.45. 200 1.40. Extreme ressure tests on N-etlioxyetlioxyetlioxypropylil(10)-meicaptop stearzimide(PC-O-No.7683) figfig 32 A lid Ae'aeear Additi 1 51 Y g S ?Test stopped because of extreme decomposition and noxious fumes.

Did not weld. None 200 1.54. None 300 2.26. None 400 2.25. 65 None 450 2.15. 500 2.15.

120 1.97. 140 22' Extreme pressure tests on N,N-dibutyl-9(10)-earbobutyoxyootade- 150 eena1nide(PC-ONo.7688) 160 Weld. 70

2 1. Applied Average scar i455 Base oil Additive load, kg. m 7683 (5%) 6 .59. 7683 (5%) 2.72. gone 7683 (5%) \leld N838 160 2.45.

None 120 Weld.

1 Test stopped because of extreme decomposition. Did not weld.

TABLE IV we glaim! d N b 1 h Evaluation of N-9, lo-epithiostearoly morpholine as an additive and as a T e compoun N my [9( 10) ydroxy' (9) 10- base oil in extreme pressure tests (ASTM D 2596-671) l u y ph ph steal'amlde- P W Base 011 afif g 321 mffif 5 No references cltedff jfif fj 128 3 33; ELBERT L. ROBERTS, Primary Examiner (5%) 160 3.25. (5%) 180 Wold, sec. CL 5% so 1.57. 260-247 .1 (5%) 2.03. 10 (5%) 2.41. (5%) 2.94. (5%) 3.00. (5%) 200 Weld, 5 sec.

N-D, IO-epithiostearoylmorpho- None 120 0.70.

line. 1 5

D0 None 200 2.13. Do None 240 2.43. D0 None 300 2.68.

Do... None 380 Weld, 50 sec.

Patent No. 3,349,454 Dated November 19, 1974 Inventor) M Frank C. Magne, Robert R. Mod Gene Sumrell and Winfred Parker It is certified that error appears n e and that said Letters Patent arc hereby corrects-:1 as shown helm-r:

Column 1, line 44, cancel "phosphorous" and insert phosphorus Column 3, line 19, cancel "N,N-dibutyloleamide" and insert N,N-dibutyllinoleamide v Line 39, cancel "(0.75 mole)" and insert (0.73 mole) Line 39, cancel "(0.72 mole)" and insert (0.73 mole) Column 4, line 63, cancel "l0NaHCO and insert 10% NaHCO Column 6, Example 19, Line 3, cancel "p.p.m." and insert RPM Example 19, Line S, cancel "ran" and insert run Signed and sealed this 13th day of May ,1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

1. THE COMPOUND N,N-DIBUTYL-(9(10)HYDROXY-(9) 10DIBUTYLPHOSPHATO)STEARAMIDE. 